Metachrome dyeing with cationic and non-ionic agents



Patented June 8, 1948 METACHRUME DYEING WITH CATIONIC AND NON-IONIC AGENTS Henry E. Millson, Plainfield, and George L. Boyer, North Plainlielcl, N. J., assignors to American Cyanamid Company, New York, N. Y., a corporation of Maine No Drawing. Application January 13, 1945, Serial No. 572,738

16 Claims. (01. 8--42') This invention relates to a new process of dye- .ing with metallizable azo dyes by the so-called metachrome process.

In the past there have been four general procedures employed in dyeing with metallizable dyes. The first utilizes pre-formed metallized dyes and requires the formation of the metallized dye before it is introduced into the dye bath. Practically all of the metallizable dyes may be utilized in this process but it is subject to a number of disadvantages. In the first place, the dye is not very efliciently used, the dye bath being poorly exhausted and the color value is not as high as desirable in some cases.

The second process is referred to as an after chrome or top chrome procedure in which the fabric is dyed with. the metallizable azo dyes and then subjected to an after treatment with a solu tion of a compound of the metal to be introduced 1 into the dye molecule.

As the name implies the dye is applied the same as an acid color and it requires an extra process and extra time forthe formation of the metallized complex.

The third procedure is the so-called Bottom chrome process in which a metal compound is first deposited in the textile fiber and then the dye is applied and the metallized complex forms in the fiber. Here again-this process is an extremely long one requiring several steps.

The fourth procedure is the so-called metachrome process in which the metallizable dye and the compound of the metal to be introduced are both present in the dye bath at the same time and the metallized dye is formed both in the fiber and in the'bath itself and not introduced as preformed compound.

The metachrome process presents many advantages. The dye is very efiectively utilized when dyeing basic fibers such as the natural animal fibers, wool, silk, and the like or synthetic fibers of similar type from casein, polyamides, and so forth. Certain dyes give good penetration and others do not. The dyes which do not give good penetration, particularly in the case of heavier shades, have therefore been considered unsuitable for use in the metachrome process and have required resort to the process starting out with the pre-formed metallized dye, the top or bottom chromev processes with their attendant disadvantages. I

According to the present invention, we have found that with dyes which normally do not show good penetration, completepenetration in the metachrome process is obtained'wherethere is present in the dye bath at least one surface 2 active agent of the cationic type, and at least one non-ionic surface active agent, belonging to the group consisting of condensation products of the polyglycols or polyalkylene oxides with higher fatty acids, higher fatty alcohols, amides of higher fatty acids, or phenols which contain longchain aliphatic substituents. In referring to higher fatty acids for the purpose of the present invention, fatty acids having 10 or more carbon atoms are included, and long-chain .alkyl substituents on phenol ethers include only alkyl groups having more than G'carbon atoms.

Cationic surface active agents are not new in the dye art. A number of these compounds have been used in various dyeing processes as dyeing assistants. They have, however, been considered unsuitable for use in a metachrome procin metallizable dyes for basic fibers. The lack of suitability was due to the fact that although somewhat increased penetration could be obtained the cationic surface active agent reacted with the acid groups of the metallizable dyes and the metal compound to form a Water insoluble complex which tended to come down on the fabric or fiber to be dyed in the form of a scum resulting in streaky and non-uniform dyeing. According to the present invention, when there-is associated with a cationic surface active agent also a non-ionic surface active agent of the groups described above, the latter appears to completely prevent scum formation and retains the dye or metal dye compound formed in the metachrome bath in a thoroughly dispersed state in which dyeings of great levelness are obtainable with all of the increased penetration made possible by the presence of the cationic surface active agent. Neither type of surface active agent'is useful in the metachrome process alone. As pointed out above, when the cationic surface active agent is used by itself, scum formation results with streaky dyeings, 0n the other hand, the non-ionic surface active agent alone will not produce the increased penetration desired. However, when the two are used together all of the penetration of the cationic material is retained and perfectly even dyeings result and in additionin many cases a surprising increase in the color value of the dye goods and in their fastnessto Washing result. This. action in no sense a'sum of the individual actions of the two types of material since neither alone will exert the desired improved penetration and levelness.

It is not desired to limit the present invention by any theory of action. However, it seems probexamples which. are

3 able that the cationic surface active agent unites with the metal compound and the metallizable acid azo dyestuff to produce some kind of a loose compound in which the surface active agent has lost its identity at least for the time being and that this whole connection is then retained in a minutely dispersed form by the surface active parts of the non-ionic surface active agent. Other factors may of course, play a part and may even be more important in producing the surprising result of the present invention which occurs in spite of the fact that the cationic surface active agent is no longer present in a free surface active form in the dye bath.

It is an important practical advantage of the present invention that it is not critical with respect to the particular cationic surface active agent used; although we have found that there is a definite advantage in using cationic agents ofthe alkylol higher alkyl guanidine salt type. These agents give optimum results and require a minimum of non-ionic surface active agents. They are, therefore, preferred although the invention is not broadly limited to their use. The choice of non-ionic surface active agents is also not critical within the specified group. There is, however, some differencein the effectiveness of the various non-ionic surface active agents included in the group, and the condensation products of polyalkyleneoxides and polymeric higher aliphatic dibasic acids give the best results with minimum amounts of agent. They are therefore, preferred. These acids are obtained by dimerizing unsaturated fatty acids particularly when conjugated to produce cyclic dibasic acids as described in the article by Bradley in Industrial and Engineering Chemistry 32, 802-803 (1940) and 33, 86-89 (1941).. It is not necessary to use any single non-ionic surface active agent; mixtures may be used.

The process of the present invention is applicable to dyeing wool, silk, polyamide, or other fabric or yarns in skein form, and the like, good results being obtained with the materials whether woven or knit and material savings are obtainable because of the stronger dyeings which result from the use of the present process. These savings may be taken by obtaining the same strength of dyeing with less actual dye or stronger dyeings with the same amount of dye and at the same time the dyeings show superior levelness, less fiber selectivity and in general improved fastness.

It is an advantage of the present invention that it is applicable to practically all of the metallizable azo dyes suitable for use in the dyeing of basic fibers, that is to say, dyes which contain acid groups such as for example sulfonic groups.

While the present invention is particularly suitable for dyeing basic fibers and achieves its greatest commercial importance in such dyeings, it is interesting to note that the invention permits the use of the metachrome process indyeing certain cellulosic material which had not been considered as suitable for dyeing with metallizable dyes by the metachrome process.

applicability to a class of fibers and fabrics which are normally not susceptible to similar processes is an additional important advantage of the present invention. 1

The invention will be described in greater {detail in conjunction with the followin specific typical, the parts being by weight.

Thus under favorable circumstances it is possible to obtain a suitabledyeing onviscose rayon. The

Example 1 Percent Glaubers salt 5 Ammonium sulfate 8 Potassium chromate 1.5

Non-ionic surface active agent (obtained by condensing a polyethylene oxide having a molecular weight of 1500 with oleic acid) 1 N'-ethanol N dodecyl guanidine acetate 0.5

The scoured, wet-out skein was entered in the cold, the dyebath brought up to the boil in about 30 minutes, and kept there for 30 minutes. Care was taken to turn the skein frequently during the initial heating period and for 15 minutes after the boil was reached- Thereafter occasional turnings of the skein were sufiicient to produce an even dyeing. 1

At the end of 30 -minutes of boiling the dyebath was brought up toits original volume by the addition of water, and 2% acetic acid (28%) was added. Boiling was continued for 30 minutes.

at the end of which time 4% of acetic acid (28%) was added, and the dyebath boiled an additional 30 minutes. The skein was then removed, rinsed in cold water, and dried. f

A dyeing prepared according to the method described in this example has many advantages over a dyeing prepared without either of the dyeing assistants. If a-dyeing is carried out with-the addition of the cationic assistant only, scumming will occur and poor uneven results will be obtained. If the non-ionic assistant alone is used, the color strength developed will not be nearly as great as that obtained whenthe cationic assistant also is added.

A metachrome dyeing obtained according to this example is superior to a metachrome dyeing as normally carried out without assistants, especially with regard'to the microscopically observed fiber levelness; in fact, the dyeing is equal or superior toa dyeing of the same chrome dyestuff applied by the sO-caIIedtopchrome procedure.

. Example 2 Per cent Glaubers salt 5 Ammonium sulfate 8 Potassium dichromate 1 Non-ionic surface active agent (obtained-by condensing 2 moles of polyethylene oxide (molecular weight 4000) and 1 mole of the dimerized acid obtained by heat treating soy bean acids and distilling off the monomeric acids) '1 N ethanol N dodecyl guanidine acetates.-- 0.5

The scoured wet-out skein was entered intothe ,cold dye bath and the dyebath brought up to the boil inabout 30 minutes and kept therefor 30 minutes. Care was taken to turn the skein frequently duringthe initial heatin periodand 2,44ey1 cc for minutes after the boil has been reached. Thereafter occasional turning of the skein was sufficient to producean even dyeing.

At the end of 30 minutes of boiling, the dyebath was brought up to its initial volume by theadditi'on of water and 2% of 28% acetic acid wasadded. Boiling was continued for 30 minutes, at the end of which time 4% of 28% acetic acid was added and the dye bath was boiled for an additional 30 minutes. The skein was then removed, rinsed in cold water and dried.

The dyeing obtained according to the method described in this example is superior to a dyeing prepared without the assistants described in this example in that it has greater color value and much better fastness to fulling, washing, alkali perspiration, light and cracking.

A dyeing made according to this example, using both the non-ionic and cationic agents is superior to the dyeing procedure in which either of the agents is used alone. By the addition of both agents in combination a dye bath is obtained which is free from scum formations at all. times during the dyeing procedure. This is nottrue if only the cationic agent is used alone. The dyeing is superior to that obtained when only the non-ionic agent alone is used in that greater color value with corresponding increase in fastness properties is obtained. The dye employed in this example is one which could not be used hitherto in the metachrome process, and hence is an example of dyes which could not be used at all in this process and have now become available by reason of the procedures of the present invention.

Example 3 0.1 part of chromable red dye (C. I. 652) was dissolved in 400 parts of water and was'suflicient to give a 2% dyeing on a wool skein having 5 parts of wool. The following agents were added to the dyebath in the order given, the percentages being based on the weight of the skein:

Per cent Glaubers salt 5 Ammonium sulfate 8 Potassium dichromate 1 The scoured wet-out skein which may be wool, was entered into the cold dye bath and the dye bath was brought up to the boil in about 30 minutes. At the end of 30 minutes at the boil, the dye bath was brought up to its original volume by the addition of water and 2% of 28% acetic acid was added. The heating was continued for another 30 minutes, at the end of which time 4% of 28% acetic acid was added and the dyeing continued at the boil for an additional 30 minutes. It is important that the skein be turned frequently during the initial period of dyeing and for about 15 minutes after boiling has commenced so that even results will be obtained. After the dyeing was complete the skein was removed from the dye bath, rinsed in cold water and dried.

A chrome dyeing prepared in this manner with the assistants described in the example gave a product which was superiorto that prepared without the assistants in that the dyeinghad greater color strength, better fiber .ievelness, and

better fastness properties in regard .to washing, fulling, .crockin'g, alkali perspiration, and..;light. Dyein'gs prepared according to this example have equal or better fastness properties than the same dyestufi dyedby the topchrome procedure, without the addition of agents.

Example 4 0.1- part of .chromablebrown dye (C. I. 98) was dissolved in 400 parts of water which was -suiiicient'for 2% dyeing on a wool skein having 'fi parts of wool. The following agents. were added to the dyebathv in the order given, the percentages beingbascd on the weight of the skein.

Per cent Glaubers salt 5 Ammonium sulfate 8 Cobalt nitrate or acetate 1 The scoured wet-out skein, which may be either wool, casein fiber, silk, rayon, or nylon, was entered into the colddyebath and the dyebath was brought up to 190-195 F. in about 20 minutes. It was then kept at this temperature for about 45 minutes. The skein was turned frequently during the initial heating up period, and less. frequently after it had reached the temperature of 190-195.

At. the end of 45 minutes at this temperature, obtained by a boiling water bath, the dyebath was brought up to its original volume by the addition of water and 2% of 28% acetic acid was added. The heatingv was continued for another 30 minutes, at the end of which time 4% of 28% acetic acid was added and. the dyeingwas continued at 190-195" for 30 minutes more. The skein was then removed, rinsed in cold water, and dried.

When casein fiber was dyed .according'to this example, there was not a very marked increase in color strength obtained, but the rate of exhaustion was better than if the dyeing was made without the agents and a more level fiber dyeing was obtained.

When silk was dyed according to this procedure, the final color strength obtained was about the same as that obtained without the addition of the dyeing agents described in this "example. However, much better penetration of the dyes into the fiber was obtained when the procedure following this example was used. In the dyeing'iby this procedure the exhaustion rate is increased a good deal by'the use of the dyeing assistants described in this example, and a saving of time in the dyeing operation was thus obtained with just as good level dyeing characteristic.

When nylon was dyed according to this example, the final color strength obtained was slightly greater than ifv dyeing assistants were not used. The penetration into the individual fibers wasv better'and thus better fastness properties were obtained; As in. the case of the silk, the dyeing rate was increased, and so a saving in time resulted by the use of the. procedure de- *example; an increase in color'strength was obtained over the dyeing'of viscous rayonwith the some in 400 parts of water making a bath sufficient for a 2% dyeing of a skein having parts ofwool by weight. The following materials were added to the dyebath in the order given, the per- .centages being given on the weight of the skein:

Per cent Glaubers salt 5 Ammonium sulfate 8 Nickel sulfate 1 Non-ionic surface active agent (obtained by condensing 2 moles polyethylene oxide (molecular weight 4000) and 1 mole of the dimerized acid obtainedby heattreating soy bean acidsand distilling oil the monomerie acids) l 1 .N ethanol N -dodecyl guanidine a cetate .0.5

A wet-out and scoured wool skein having 5 parts of wool was introduced into the cold dyebath and the dyebath was brought up to the boil in about 30 minutes and kept there foran additional 30 minutes. During this time the skein' was'frequently turned, especially during the heating up period, so that even dyeing of the skein was obtained. Afterjthe initial heating up period, the

turning need not be so rapid as at the very beginning. At the end of 30 minutes of boiling, the dyebath was brought up to itsoriginal volume by the addition of water and 2% of 28% acetic acid was added. Boiling was then continued for an additional 30 minutes at the end of which time 4% more of the 28% acetic acid was added and the dyebathboiled for 30 minutes more. At the end of this time, the skein was removed from the dyebath, rinsed in cold water and dried. j

A dyeing prepared in this manner with the 'assistants'gave a product which was superior to that prepared without the assistants in that it had greater color strength; better fiber levelness, and better fastness to washing.

7 Example 6 0.1. part of a dye formed by coupling nitroaminophenol on metaphenylene diamine, diazotizing and then coupling to Cleves acid was dissolved in ,400 parts of water making a bath suflicient fora 2% dyeing of a skein having 5 parts of wool by weight. The following materials were added to the dyebath in the order given, the

percentages being given on the weight of the skein: V t

1 Per cent Glaubers salt 5 Ammonium sulfate I 8 -Nickel sulfate 1 Non-ionic surface active agent (obtained by l condensing 2 moles of polyethylene oxide" (molecular weight 1500) and 2 moles of longer.

The scoured wet-out wool'skein was entered into the cold dyebath and the dyebath broughtupto the boil in about 30, minutes andikept there for 30 minutes. a This skein was turned frequently during the initial heating period and for 15 minutes after reaching the boi1,.s0 that goodpenetration throughout the threads was obtained. Thereafter, only occasional turning of the skein was necessary to produce an even dyeing;

At the end of 30 minutes of boiling the dyebath was brought up toits original volume by the addition of'water and 2% of 28% acetic acid .was added. After continued boiling for 30minutes another addition of 4% of 23% acetic-acid was added and the dyebath was'boiled. for 30'minutes The skein was thenremoved, rinsed in cold water, and dried. 1

A dyeing prepared according to this example showed greater color value and had better fastness to light, washing and crocking than a dyeing'prepared without the-addition of the .dyeing assistants mentioned in this example. A dyeing prepared by this example also exhausted much more rapidly, giving a complete metallization in a shorterperiod of time, while good dye levelness was obtained. Cross sectional microscopical .examination showed than when this procedure was used much better level fiber dyeing was obtained.

Example 7 A bath was prepared with the same proportions of materials'as in Example 2 but 1 partof "nonionic surface active agent was mixed with 2 parts of the dyestufi and one part of the sodium sulfate to give a dry powder. 'Ihispowder was then dissolved in water andthe remaining ingredients added. The dyeing procedure was the same as that in Example 2 and the results obtained were comparable.

This modification has the advantage that the non-ionic surface active agent may be sold as partof a dry dye composition;

Example 8 A composition corresponding to Example 4 was prepared but the non-ionic surface active agent and the cationic surface active agent were'mixed with the dye which maybe the brown dye 10f Example 4'cr to the red dye of Examples 1 and 3, forming a powder or a dye paste. This paste was then added to water to make a dyebath of the same concentration. as in Example 4 except that the cobalt nitrate was substituted by'a corresponding amount of potassium dichrom'ate. The dyeing procedure of Example 3 was then followed and the results were comparable.

- Example!) 7 7 0.1 partof chromable black dye, (C. I. 203) .was dissolved in 400 parts of water and was sufiicient to give a 2% dyeing on a piece of wool flannel having 5 parts of wool., The following agents were added to the dyebath in the order given, the percentages being based on the weight ofthewool: -1 Per cent .Glaubers salt' .5 Ammonium sulfate. 8 Condensation product of more than 4 molsf of polyethyleneoxides with oleyl alcohol; 1 Potassium dichromate 1 Nethanol N dodecyl guanidine acetateeufl 0.5

The'scoured' wet-out piece of wool wasentered i into the cold dyebath and the dye bathflbrought up to the boil in about 30 minutesandikept there 1 i for 30minutes. Care was taken to stir the. dyeing frequently during the initial heating periodand for 15- minutes after the boil has been reached Thereafter occasional stirring of the dyeing was sufficient to produce an even dyeing.

At the endiof 30 minutes of boiling, the dye-' bath was brought up to its initial volume. by the addition. of water,. and 2% of 28% acetic acid was added. Boiling was continued for 30 minutes, at the end of which. time 4% of 28% acetic acid was added and the dyebath was boiled for an additional 30 minutes. The cloth was removed,v rinsed in cold water and dried.

Example 1 A dyeing was made according' to. Example 9 except 0.1 part of chromable dye (C. I. 202) was used together with the following agents:

Per cent Glaubers salt Ammonium sulfate 8 Potassium dichromate 1 Nomionic surface active agent (obtained by condensing 2 mole of polyethylene oxide (molecular weight 4000) and 1 mole of the dimerized acid obtained by heat treating soy bean acidsand'v distilling off the monomeric acids)- 1 N ethanol N dodecyl guanidine acetate 0.5

Example 11 A dyeing was made according to Example 9, except 0.1 part ofchromable red. dye (C. I. 652) was used, together with the following agents:

Per cent Glaubers salt 5 Ammonium sulfate 8 Potassium dichromate 1 Condensation product of more than 4 mole of polyethylene oxides-with oleyl' alcohol 10 Cctyl trimet'hyl ammonium bromide 0.5

Example 12 A dyeing was made according to Example 9, except 0.1 part of chromable black dye (C. I. 203) was used together with the following agents:

Per cent Glaubers salt 5 Ammonium sulfate 8 Potassium dichromate 1 Condensation product of more. than 4 mols of polyethylene oxides with oley-l alcohol 1 Cetyl trimethyl ammonium bromide 0.5

Example 13 0.1 part of. chromable red dye ('C. I. 652) was dissolved in 4500 parts of water which was sufiicient to give a 2% dyeing on 5 parts of wool. To this dye bath the following materials were added in the order given, based on the weight of the wool":

5% Glaubers salt 8% ammonium sulfate 1% potassium dichromate 1% of a non-ionic surface active agent having the following formula:

( MHQOO( HZCHlObOHlOHQOH) 0.5% is a condensation product of 1 mol of octadecyl guanidine bicarbonate and 6 mols of ethylene oxide The wool which had been previously wet out was entered into the dyebath which was then brought up to the boil in 30 minutes. After Example 14 0.1 part of chromable dye (C. I. 202) was dissolved in 400 parts of water which was sufficient to give a 2% dyeing on 5 parts of wool. To this dye bath the following materials were added in the order given, based on the weight of the wool:

5% Glaubers salt 8% ammonium sulfate 1% potassium dichromate 1 of a non-ionic surface active agent havingv the formula which appears below which is prepared by condensing of triethylene glycol with acrylonitrile, hydrogenating to the amine and condensing with lauric acid to form the amide.

(C11H23CONHCsI-IcOCzI-ROCzHsOCaI-IsOI-I) The wool which had been previously wet out was entered into the dye bath which was then brought up to the boil in 30 minutes. After boiling for 30 minutes, 2% of 28% of acetic acid was added and the boiling continued for an additional 30 minutes. At this time 4% more of 28% acetic acid was added and the wool was boiled for 30 additional: minutes. It was then removed from the dyebath, rinsed in cold water and dried. During the initial dyeing period, the wool should be turned frequently so that even dyeings are obtained.

While all of the n0n-ionic surface active agents covered by the present invention are chemically condensation products of polyglycols, in the manufacture of some of them, the reaction is with an alkylene oxide which forms the polyglycols during the condensation reaction. The term condensation product of polyglycols is therefore used to describe the chemical constitution of the final product and not as a limitation to the process by which the product may have been produced.

It will be noted in most of the examples that the non-ionic surface active agent is added to the dye bath before incorporating the cationic surface active agent. The invention is not limited to this exactprocedure. However, it does have advantages in most. cases and the best results are usually obtained by following this order of introduction of the surface active agents and therefore this constitutes a preferred method.

In the examples, dyeings' with chromium, copper, cobalt and nickel dyes are described. The invention, however, is not limited to the use of these particular metals. On the contrary, other metals capable of forming complexes may be used such iron, aluminum, tin, cadmium, zinc, mercury, tungsten, manganese, zirconium, titanium, lead, molybdenum, antimony, tellurium, vanadium; and the combinations: chromium copper, chromium-aluminum, chromium-manganese, chromium-cobalt, chromium-vanadium, copper-vanadium, chromium-nickel, chromium-iron, copperzinc, chromium-titanium, chromium-tin, aluminum-tin, copper-iron combinations of metals react with the dye to produce a product which is 11 no't'identical with the mixture of the products obtained by treating portions of the dye with the separate metals.

This application is in part a continuation of our co-pending application Serial No. 420,504, filed November 26, 1941, now abandoned.

We claim;

1. A method of dyeing material by the metachrome process which comprises subjecting the material to be dyed to the action of a dye bath containing a metallizable azo dye having acid groups suitablefor dyeing the material, a compound of a metal capable of metallizing thedye, a cationic surface active agent and a non-ionic surface active agent selected from the group consisting of condensation products of polyglycols with higher fatty acids, condensation products of polyglycols with higher fatty alcohols, condensation products of polyglycols with amides of higher fatty acids, and condensation products of polyglycols with long-chain alkyl substituted phenols.

2. A method of dyeing basic nitrogenous fibers by the metachrome process which comprises-subjecting the material to be dyed to the action of a dye bath containing a metallizable azo dye having acid groups suitable for dyeing the material, a compound of a metal capable of metallizing the dye, a cationic surface active agent and a nonionic surface active agent selected from the group consisting of condensation products of polyglycols With higher fatty acids, condensation products of polyglycols with higher fatty alcohols, condensation products of polyglycols with amides of higher fatty acids, and condensation products of polyglycols with long-chain alkyl substituted phenolsv alkyl substituted phenols.

' 4. A method of dyeing basic nitrogenous fibers by the metachrome process which comprises subjecting the material to be dyed to the action of a dye bath containing a metallizable azo dye having acid groups suitable'for dyeing the material, a compound of a metal capable of metallizing the dye, an alkylol higher alkyl guanidine salt and a non-ionic surface active agent selected from the group consisting of condensation products of polyglycols with higher fatty acids, condensation products of polyglycols with higher fatty alcohols, condensation products of polyglycols with amides of higher fatty acids, and condensation 12 products of polyglycols with long-chain alkyl s'ubstituted phenols.- 5. Amethod according to claim 1 in which the bath is prepared by dissolving the dyestuii' 'the metal compound,'the non-ionic'surface activeagent, and the cationic surface active agent-"in the order given. a 6. A method according bath is prepared by dissolving the dyestuff, the metal compound, the non-ionic surface activeagent and the alkylol higher alkyl guanidine salt in the order given.

7. A method according to claim 1 in which the non-ionic surface active agent is a condensation d product of a polyethylene oxide and a dimerfaci obtained by heat-treating fatty acids havingjcon jugated double bondsand removing the monoa meric acids by distillation;

8. A method according to claim 2 in which the non-ionic surface active agent is a condensation product of a polyethylene oxide and a dimer acid obtained by heat-treating fatty acids having conjugated double bonds and removingthe mono meric acids by distillation.

9. A method according to claim 1 in which the material is cellulosic.

10. A method according-t0 claim 2' in which the metal compound is a chromium compound.

11. A method according to claim 2'in which the metal compound-15a chromium compound.

12. A method according to claim 3 inwhich the metal compound is a chromium compound, 13. A method according to claim' 1 in which the metal compound is a cobalt compound.

14. A method according to claim 2 in which the metal compound is a cobalt compound.

15. A methodaccording to claim 3 in-which the metal compound is a cobalt compound.

16. A method according to claim 1 in which" a nickel compound. HENRY E. MILLSON. GEORGE L. ROYER.

the metal compound is REFERENCES CITED The following references. are of record the;

file of this patent:

V UNITED STATES PATENTS to claim '3 in whichthe France Sept. 6, 1937 

